Process of carroting animal fiber and the like and composition therefor



Patented Jan. 17, 1939 I UNITED STATES PATENT O FIE PROCESS OF CARROTING ANIMAL-FIBER L AND THE LIKEANDCOMPOSITION TH ERE- 'FOR Constantine F. Fabian, Brookfield, Conn., and

Alexander N. 'Sachane'n, Woodbury, N. J., as-

signors to The Non-Mercuric Carrot Company; Danbury, Conn, a corporation of Connecticut No Drawing. Application Octoberl'l, 193s,

, Serial No. 235,482

9 Claims. (01. 8-412 -This invention relates to the carroting of animal fiber and hasfor its object the carroting. of fur under such conditions and with a solution of such composition that the fur has imparted tov it the capacityof producing a strong, firm and tight felt, without impairment of the life and :strength of the fibers or undesirable discoloration of the natural color of the hair. 1

- The carroting process as commonly carried'out ,10 isv eflfected by reactions of a hydrolyzing and an oxidizing nature: which are intended to act on the albuminoids of .theouter layers of the fiber.,

In the application of such carroting solutions as .commonly carried out, however, this hydrolyzation and oxidization are found to act on the natural pigment which gives the .fur its characteristic color andthe particles of which are distributed. through the fibrils of'keratin of which the body of the animalfiber is composed.

I This results in the destruction or decomposition of the pigment, leadingnot only to a detrimental discoloration of the furbut to a weakening otthe mechanical structure of. the fibers.

, For example, with the ordinary mercurynitrate acid carroting'solution-white fur turns 40 be successfully produced. I

This destruction of the pigment is alsohighly objectionable since it 'appreciably impairs the uality of the iurfor'feltingv It is well known that fur'discolored in carroting results in irregu-, -i5 larity in shrinkage in diminished strength and firmness, and in the life-of the resulting felt.,

It wouldappear that the natural pigment'is deposited between the fibrils of the keratin lying relatively deep in the'fiber body and doubtless.

50 penetrating the intermolecular spaces of the colloidal soiidsof the fiber, so that, besides giving the'furitscharacteristic color, it serves as a cohesive agent', providing coherence between the fibrils and adding to the life-and strength-of the 55* fibers. The result is, that when the carroting Light colors, such as fsteel; silvertone, etc., cannotsolution destroys or decomposes the pigment, the cohesion of. the fibrils is afiected and the body' of the fiber-becomes mechanically weaker. At all events, it has been found that the destruction of the naturalpigment in whole or in part is detri- 5 mental both to the. shrinking capacity of the fur and to the firmness, life and color of the resulting felt.

We have discovered that discoloration of and impairmentin the strength of the fur maybe 10 avoided by including in the carroting solution, and in the presence of an acid hydrolyzing agent and an oxidizing agentjsuch substances as preserve the'natural pigment against decomposition while permitting the hydroly'zing andv oxidizing '15 reactions necessary for carroting to take place,

v thereby leaving the carroted fur undiscolored'and with its characteristic natural colorjunimp'aired in strength.

I For such substances, which act as protecting 20 agents for the natural pigment, wehavefound 4 available low concentrations of certain water- 'soluble' organic dye compounds oi high molecular weight, which are stable in the carroting solution 1 and have a directjaflinity to animalv fibers. 5

We believe thatthe decomposition of the natural pigment results mainly from the oxidation of the pigment by the oxidizer in the carrotingsoiution and that the pigment protecting agents referred'to act as anti-oxidants, preventing oxidation of the natural pigment while permitting the required carrotin'g action totake place. Whether or not this is the correct explanation, we have found that the treatment of the fur with carroting solutions containing such agents leaves. the cars '35 roted fur withv its natural color unimpaired, so

.that the felt tormed-therefrom may be subsequently dyed with the exact} desired shades with-. outdeparture therefrom, without dullness in color, and without yellow or' undesirable back- 40 ground. 1 It furthermore leaves the fur without the impairment in strength previously experienced through discoloration, eliminating irregularity in shrinkage, improving the rate of shrinking, and producing a superior tighter, mor durable, and liner felt. u I

Organic compounds suitable for use are those characterized by having the chromophore group or capable of forming such group with the-oxidizer of the carroting solution and further char- 5o acterized by a salt forming group. Such comypounds for use as pigment protecting. agentsshould be water-soluble, of high molecular weight, "capable of remainingstable and without decomposition in the presence of the acid hydroiyzing 1 4:8-diethylamino- 1:5- dihydroxyanthraquinone- 2:6-disulphonic acid (CisHicNzOioszNaz);

sodium salt of l-amino-2-methy1-4-o-sulpho-pphenyltriamino groups, derivatives of anthraquinone containing an additional ring'having a nitrogen atom and having quinoline character, derivatives of naphthalene containing a pyrcnine ring, derivatives of triphenylcarbinol in the sub-classes of derivatives of pararosanilineand rosaniline, and azonaphthalene derivatives.

As examples of derivatives of anthraquinone there may be instanced the following: Sodium salt of 4:8 diamino-l:5-dihydroxyanthraquinone- 2:6-disulphonic acid (C14HaN2O1oS2Na2); sodium bisulphite of 1:2-dihydroxyanthraquinone-pquinoline '(C17H9NO4+2NaHSO3); sodium salt of and tolylaminoanthraquinone (CzzI-InNgOsSNa)! As examples of derivatives of naphthalene there may be instanced the following: Sodium salt of sulphodiethoxydiphenyldiamino-o-carboxydichloro-phenyl-xanthenyl (CaeEsNzOaSNiizt'ila); sodium salt of sulphodiphenyl-diamino-o-carboxyphenyl-xanthenyl Ca zH2oN2OcSNa2); and sodium salt ofastetraethyldiamino-sulpho-phenyl-xanthenyl sulphonate (CzvHzaNzO-aSzNa).

examples of derivatives of triphenylcarbinol may be instanced the following: Sodium salt of diphenyltriamino-diphenyltolyl-carbinol sulphonic acid (CazHzaNaO-rSNa); hydrochloride of tetramethylphenyltriamino diphenyl a. naphthyl-carbinol anhydride (C35H32N3Cl); sodium salt of triphenyltriamino-triphenylcarbinol anhydride (CazHasNaOsSaNaz); sodium salt of tritriphenylcarbinol disulphonic acid anhydride (cz'lHzaNaoeszNa); hydrochloride of tetramethylethyltriamino-diphenyl-a-naphthylcarbinol anhydride (CzeHazNsCl) and calcium salt of disulphonic acid of m'-h ydroxytetraethyldiamino-triphenylcarbinol anhydride As examples of azo-naphthalene derivatives usable as such pigment protecting agents may be instanced the following: Sodium salt of 3:6 disulpho- 8 -hydroxy-(la-naphthalene azo-p tolyl-- naphthylamine-S-sulphonio acid (ca'lHlaNsOiosaNaa) sodium salt of 3:6-disulpho-8-hydroxy-a-naphthalene-azo--amino-l naphthol I (CzbHraNsOaSzNaz);

and sodium salt of 3:6-disulpho-8-hydroxyunaphthalene-azo-phenyl-a-naphthylamine 8-sulphonic acid (CzcHieNaoioS aNaz).

The primary function of such agents is topro tect the pigment against decomposition and not to serve as mere dyes and these compounds are.

usually employed in relatively low concentrations; much less than those employed where these compounds are intended to have dyeing properties. It will also be noted that these dye comperiods of time.

pounds are utilized in the carroting treatment under conditions which prevent any actual dyeing effect. They are used in the presence of an oxidizer and with the absence of boiling, either of which'conditions in the case of this particular class of dyes precludes a permanent dyeing effect on the animal fibers.

We prefer to employ concentrations represented by arange of from 0.05% to 0.3% by Y weight with respect to the weight of the carrot-v ing solution, or in, some cases concentrations of lessthan 0.05% may be employed. In carrying out the present invention as herein described,

a slight temporary discoloration or tinge may soiii imes be left on the fur, but should this at '1 iplace, such tinge is easily removed by washing 'with water, such as the washings to which the formed hats are later subjected. It is to be noted, however, that the protecting agent or dye, in the presence of the other compounds of the solution and in the low concentrations 'employed, produces no permanent or fixed dyeing effect on the fibers of the fur and no perma nently fixed stain or-discoloration on the fur,

and such protecting agents or dyes, even though producing a temporary discoloration such as referred to, are thus considered to be and are referred to herein as dyes ofa non dyeing character. The variation in concentration of such agents will depend on the nature of the fur and the character of the natural pigment in the fur. For example, for black or dark fur a greater concentration ordinarily would be used, and for lighter fur a lesser concentration. In some cases a' plurality of these pigment protecting agents- .may be used.

For the hydrolyzing agent there may be used one or more acids, either inorganic or organic, capable of having a hydrolyzing reaction, such, for example, as sulphuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, etc. In

' some cases the hydrolyzing agent may comprise a plurality of acids. For the acid hydrolyzing agent in place of the hydrolyzing acids, or in the same solution with such'acids, there may be employed suitable acid salts, such, for example, as primary sodium phosphate (NaHzPOnHzO), or sodium bisulphate (NaHSO4.I-I2O).

For oxidizers there may be employed one or more of any oxidizing agents which give a sufficiently strong oxidizing action, such, for example, as hydrogen peroxide, persulphates, perchlorates, organic peroxides, etc.,'

Where hydrogen peroxide is employed as an oxidizer, it is desirable to make use ofa small quantity of some form of stabilizing agent. Fur on the skins contains more or less dust and even particlesof metal accumulated during the preceding processing of the skins. These foreign particles tend rapidly to accelerate the decomposition of hydrogen peroxide, so that when the solution is brushed on the skin the hydrogen peroxide is apt rapidly to decompose, resulting in inadequate and non-uniform'oxidation of the fiber.

position of hydrogen peroxide is greatly decreased, resulting in such stability of the carroting solution that its oxidizing strengthen the. skins is greatly intensified, the oxidizing action prolonged, and the solution itself can be stored for long The stabilizing agents forthis In the presence of certain "inorganic and organic stabilizing substances, the rate of decompurpose are numerous, including, for'example, sodium metaphosphate, phenacetin, sodium salicylate, citric acid. urea. etc. These stabilizing agents need be employed in minute percentages irig agent;,Although, 'for' hygienic reasons, we 1 ,wetting of the fur comprise, for example "(as described in our'prior'Patent No. 2,087,854), watersoluble I organic, "oxygen, nitrogen and sulphur for the sole purpose of stabilizing the hydrogen only, are without carrotin g 'efi e'ct, and are added peroxide; Preferably a combination of two such stabilizers isemployed, for examplegsddium metaphate and-fsodium' salicylate, or citric acid nd urea., x W

a suitable acid hydrolyzing' agent and'an oxidizp'ref er f' to employ carroting solutions ,in which i g mercury is absent,'the; pigment" protecting agents 15 described,may be used in solutions containing "tionand'imp'airment of thefuri However, 'we' have ifound thatthe effectiveness Yof such pigment protecting agents'ls materially increased by, their presenceandjaction jointly inthe same solution with other inhibitors which ,we have heretofore employed for the checking f, of excessive 'carrotinglactions in the wetting and H drying of th containing compounds, such as alcohol; aldeih'y des, ketones, carbo a'cids', airlines, 'tetrazines i and'hete'rogcyclic compounds," 'sulpho acidsand sulphin'o acids, present in such" amount in the solution as to prevent excessive carroting action on Jth ei part of the oxidizing agent and thel'iy- V drolyzer; ,1

, Inhibiting" compounds efiective in protecting the fur against excessive I carrotirig "during 'drying and storage-las described in our prior Patent No. 2,048,645,) comprise water-soluble,substane'" tially. neutral salts of strong inorganicacids and strong bases, preferably saltsof polybasic 'inor- 5 ganic acids and alkali metal or alkaline earths, j, such as sodium sulphate, potassium chloride,bi-

sodium phosphate, ammonium sulphate, calcium chloride and'bisodium sulphate.

Accordingly, for-the 1b st carroting effect, re-' sulting in the preservation of the fur in unimpairedcondition, with the speediest and most forming of the felt, and a felt of best quality, we make use in the same solution of the described pigment protecting agents in combina- "tion' with the other organic and inorganic inhib-j.

itors referred to.

be had while checking or inhibiting excessive carroting reactions of all kinds, particularly where the hydrolyzing and oxidizing. agents are in such concentrations as to be'harmfjul to, the

fur if used alone, resultingein an unimpaired fur fiber, quick shrinking, strong and durable felt,

and improved color of the felted fur in dyeing.

The application to the-animal fibers of the carroting solution containing: the pigment prothe solution being maintained at normal room temperature. It may, however, be applied to the fur by spraying it on the uncut. fur, or the fur itself, after having been cut from the skin, may

have the carroting solution applied by immersing the fur in the same, or otherwise. Y

. eemege' of the pigment protecting compounds ofthe'nature described may beused ef fectively with any carroting solution' containing ercury with the effect of prevntirigdiscolorag a which aregiven in percentages ,of the total weight ofthe solution.

, Sodium salt of 9:8 diamino-l;5 dmydroxy- V Such inhibiting compounds effective, during the regular rate of shrinkage in the subsequent The fur carrotedas described by brushing is subsequently dried and cut and the cut fur subthe fo'rmedand shrunken felt, etc. I

, This invention will be best understood by the 7 following specific examplesof c'arroting solutions which maybe prepared according to the general principles of our. invention and intended forap 'plication to the animal'fibers on the skins. [It

will be understood that fin these examples the carroting; composition, comprises an sequeous solutionhaving parts. by weight, of water with the :chmicalsubstances named, thenweights of Crystalline sodium sulphate- Sodium metapho'sphate pho-p-tolylamino-anthraquinone (CzzHi'lNzoasNa) s.....-... 0.2

I J Example 4- Sulphuric acid (Tech.93%) 5.5 Crystalline sodium sulphate; 4 Ethyl alcohol 2 Nitric a 1 Hydrogen peroxide 5 Sodium salt of 4:8-diethylamino- :S-dihydroxyanthraquinone,- 2 6 dlsulphonic gacid (CraHmNzOmSnNas) 0.2

' Example 5 I Phosphoric acid '7 Sulphuric acid 3 Crystalline sodium sulphate 4 Acetone 5 Hydrogen peroxide 6 f Sodium salt "of sulpho-diethox ydiphenyldiamino o carboxydichlorophenyl xan thenyl (CasHzeNzOaSNazCln) ---0.1

Example 6 Sulphuric acid 6.5, Crystalline sodium sulphate 5 Succinic acid 2 Hydrogen peroxide 6 Sodium salt of diphenyltriaminmdiphenyltolyl-carblnol s u 1 p h o n i- 0 acid '(CazI-IzaNaO4SNai (colorless, carbinol) Ethyl alcohol -III:II'I"I V4 7 This application is a continuation 'ln'part of our prior, co-pending application, Serial No. 189,614, filed February 9, 1938a" V Various changes in and departures from the embodiment of our carroting compositions may 7 'bemade as the same have been heretofore exemplified,ia1l within the scopeof our generic insense.

We claim:

I 1. An aqueous carrotlng-solution' for treating,

animal fiber or the llke containing, each in the presence of the other, an'acid hydrolyzing agent, an oxidizing agent and; a protecting agentrfor g 9. A carroting solution as defined in claim 1, g in which'for the pigment'protecting agent there is employed sodium salt of diphenyltriamino-db' the natural pigment; the latter comprising a water-soluble organic acid dye of, a non-dyeing character in the presence of other ingredients of thesolution, of high molecular weight, having direct aflinity to animal fibers, and'containing a salt forming group, said protecting agentbeing' stable in said solution and being further characterized by having in said solution the chromopigment of the fiber.

of the total weight ofrthe solution; 7

' ,5; A carrotingosolution as phenyltolyl-carbinol sulphonic acid 2.- A carroting solution as defined in claim 1,

V in whichthe pigment'protecting agent is present in a concentration not exceeding by weight 0.3%

3. A carroting-solution as defined in claim 1,

in which for the pigment protecting agent .there is employed a derivative of anthraqui'nonei;

4. A ,carroting solution as defined in claim 1,

f in which for the pigment protecting agent there isiemployed a derivativeof naphthalene contain-1 inga pyroninering';

defined in claim 1,

, in which for the pigment protecting agent there is gemployed-a derivative of triphenylcarbinol."

. 6'. The process of preparing fur and the like sforfelting, which consists in brushing theiur with an aqueous carrotin g solution containing an Lacidhydrolyzing agent andan oxidizing agent, ,1 andprotecting the natural plgmentin the body of the fur fiber against decomposition under the i action of the. carrotinjgisolution bythe presence in the solution of a water-soluble organic acid dyeof a nondyeing icharacter in the presence ofthe other ingredients of the solution, of high molecular weight, stable in said solution, having in said solutlonthe chromophorefgroup;

H 7 '7.'A]carroting solution as defined in claim 1,

in which" for the pigment protecting agent there thenyl (CgsHzeNaOtSNazClz) xmmaroolsmr.

CONSTANTINE F. r N. SAQHANEN.

direct aillnity tov animalfibers-and containing a' salt forminggroup and characterizedgby having 

